U.S. patent application number 10/894327 was filed with the patent office on 2006-01-19 for additives and lubricant formulations for improved antiwear properties.
Invention is credited to Christopher J. Dudding, Carl K. JR. Esche, Anthony Fagan, Peter Growcott, Andrew Robertson.
Application Number | 20060014651 10/894327 |
Document ID | / |
Family ID | 35600184 |
Filed Date | 2006-01-19 |
United States Patent
Application |
20060014651 |
Kind Code |
A1 |
Esche; Carl K. JR. ; et
al. |
January 19, 2006 |
Additives and lubricant formulations for improved antiwear
properties
Abstract
A lubricated surface and method for reducing wear between metal
parts. The lubricated surface contains a base oil of lubricating
viscosity and an amount of a hydrocarbon soluble titanium compound
effective to provide a reduction in surface wear greater than a
surface wear of a lubricant composition devoid of the hydrocarbon
soluble titanium compound.
Inventors: |
Esche; Carl K. JR.;
(Richmond, VA) ; Dudding; Christopher J.;
(Reading, GB) ; Growcott; Peter; (Hartley Wintney,
GB) ; Fagan; Anthony; (Chesterfield, VA) ;
Robertson; Andrew; (Bracknell, GB) |
Correspondence
Address: |
DENNIS H. RAINEAR
CHIEF PATENT COUNSEL, ETHYL CORPORATION
330 SOUTH FOURTH STREET
RICHMOND
VA
23219
US
|
Family ID: |
35600184 |
Appl. No.: |
10/894327 |
Filed: |
July 19, 2004 |
Current U.S.
Class: |
508/162 |
Current CPC
Class: |
C10M 137/06 20130101;
C10M 129/14 20130101; C10M 2223/042 20130101; C10M 135/10 20130101;
C10M 2207/021 20130101; C10N 2030/06 20130101; C10N 2040/255
20200501; C10M 129/40 20130101; C10N 2010/08 20130101; C10M
2219/044 20130101; C10N 2040/252 20200501; C10N 2070/02 20200501;
C10M 129/06 20130101; C10M 2207/027 20130101; C10M 2207/126
20130101 |
Class at
Publication: |
508/162 |
International
Class: |
C10M 141/10 20060101
C10M141/10 |
Claims
1. A lubricated surface comprising an antiwear coating of a
lubricant composition containing a base oil of lubricating
viscosity and an amount of a hydrocarbon soluble titanium compound
effective to provide a reduction in surface wear greater than a
surface wear of a lubricant composition devoid of the hydrocarbon
soluble titanium compound.
2. The lubricated surface of claim 1, wherein the lubricated
surface comprises an engine drive train.
3. The lubricated surface of claim 1, wherein the lubricated
surface comprises an internal surface or component of an internal
combustion engine.
4. The lubricated surface of claim 1, wherein the lubricated
surface comprises an internal surface or component of a compression
ignition engine.
5. The lubricated surface of claim 1, wherein the amount of
hydrocarbon soluble titanium compound provides an amount of
titanium metal ranging from about 50 to about 500 ppm in the
lubricant composition.
6. The lubricated surface of claim 1, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
titanium compounds derived from organic acids, alcohols, and
glycols.
7. The lubricated surface of claim 1, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
titanium carboxylates, titanium phenates, titanium alkoxides,
titanium phosphates, and titanium sulfonates.
8. A motor vehicle comprising the lubricated surface of claim
1.
9. A vehicle having moving parts and containing a lubricant for
lubricating the moving parts, the lubricant comprising an oil of
lubricating viscosity and an amount of a hydrocarbon soluble
titanium compound effective to provide a reduction in surface wear
of the moving parts greater than a surface wear of the moving parts
provided a lubricant devoid of the hydrocarbon soluble titanium
compound.
10. The vehicle of claim 9, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of a
titanium compound derived from organic acids, alcohols, and
glycols.
11. The vehicle of claim 10, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of titanium
carboxylates, titanium phenates, titanium alkoxides, titanium
phosphates, and titanium sulfonates.
12. The vehicle of claim 8, wherein the moving parts comprise a
heavy duty diesel engine.
13. A fully formulated lubricant composition comprising a base oil
component of lubricating viscosity, an amount of hydrocarbon
soluble titanium-containing agent effective to provide a reduction
in an amount of phosphorus or sulfur antiwear agent needed in the
lubricant composition to provide substantially equivalent wear
performance in the absence of the titanium-containing agent.
14. The lubricant composition of claim 13 wherein the lubricant
composition comprises a low ash, low sulfur, and low phosphorus
lubricant composition suitable for compression ignition
engines.
15. The lubricant composition of claim 13, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
a titanium compound derived from organic acids, alcohols, and
glycols.
16. The lubricant composition of claim 15, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
titanium carboxylates, titanium phenates, titanium alkoxides,
titanium phosphates, and titanium sulfonates.
17. A method of reducing wear of metal parts in an engine
comprising contacting the engine parts with a lubricant composition
comprising a base oil component of lubricating viscosity and from
about 50 to about 500 parts per million titanium in the form of a
hydrocarbon soluble titanium compound.
18. The method of claim 17 wherein the engine comprises a heavy
duty diesel engine.
19. The method of claim 17, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of a
titanium compound derived from organic acids, alcohols, and
glycols.
20. The method of claim 19, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of titanium
carboxylates, titanium phenates, titanium alkoxides, titanium
phosphates, and titanium sulfonates.
21. A lubricant additive concentrate for providing improved
antiwear properties to a lubricant composition comprising the
concentrate and a hydrocarbyl carrier fluid, the concentrate
comprising an amount of a hydrocarbon soluble titanium compound
sufficient to provide an antiwear performance for the lubricant
composition greater than an antiwear performance of a lubricant
composition devoid of the hydrocarbon soluble titanium
compound.
22. The additive concentrate of claim 21, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
a titanium compound derived from organic acids, alcohols, and
glycols.
23. The additive concentrate of claim 22, wherein the hydrocarbon
soluble titanium compound is selected from the group consisting of
titanium carboxylates, titanium phenates, titanium alkoxides,
titanium phosphates, and titanium sulfonates.
24. A lubricant composition comprising a base oil and the additive
concentrate of claim 21.
25. A method of lubricating moving parts with a lubricating oil
exhibiting increased antiwear properties, the method comprising
using as the lubricating oil for one or more moving parts a
lubricant composition containing a base oil and an antiwear
additive, the antiwear additive comprising a hydrocarbyl carrier
fluid and an amount of hydrocarbon soluble titanium compound
providing from about 50 to about 500 parts per million titanium in
the lubricating oil.
26. The method of claim 25, wherein the moving parts comprise
moving parts of an engine.
27. The method of claim 25, wherein the engine is selected from the
group consisting of a compression ignition engine and a spark
ignition engine.
28. The method of claim 25, wherein the engine includes an internal
combustion engine having a crankcase and wherein the lubricating
oil comprises a crankcase oil present in the crankcase of the
engine.
29. The method of claim 25, wherein the lubricating oil comprises a
drive train lubricant present in a drive train of a vehicle
containing the engine.
30. The method of claim 21, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of a
titanium compound derived from organic acids, alcohols, and
glycols.
31. The method of claim 30, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of titanium
carboxylates, titanium phenates, titanium alkoxides, titanium
phosphates, and titanium sulfonates.
32. A metal surface comprising a wear reducing amount of an
oleaginous composition containing an amount of titanium provided by
a hydrocarbon soluble titanium compound sufficient to reduce metal
surface wear to less than an amount of metal surface wear in the
absence of titanium.
33. The metal surface of claim 32, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of a
titanium compound derived from organic acids, alcohols, and
glycols.
34. The metal surface of claim 33, wherein the hydrocarbon soluble
titanium compound is selected from the group consisting of titanium
carboxylates, titanium phenates, titanium alkoxides, titanium
phosphates, and titanium sulfonates.
35. The metal surface of claim 32, further comprising an amount of
phosphorus and sulfur antiwear agents which is less than an amount
of phosphorus and sulfur antiwear agents for substantially
equivalent wear performance in the absence of the hydrocarbon
soluble titanium compound.
36. The vehicle of claim 9, wherein the amount of hydrocarbon
soluble titanium compound provides from about 50 to about 500 parts
per million titanium metal in the lubricant.
37. The lubricant composition of claim 13, wherein the amount of
hydrocarbon soluble titanium-containing agent provides from about
50 to about 500 parts per million titanium metal.
38. The lubricant additive concentrate of claim 21, wherein the
amount of hydrocarbon soluble titanium compound in the concentrate
is sufficient to provide from about 50 to about 500 parts per
million titanium to a lubricant composition containing the
concentrate and carrier fluid.
39. The metal surface of claim 32, wherein the oleaginous
composition contains from about 50 to about 500 parts per million
titanium provided by the hydrocarbon soluble titanium compound.
Description
TECHNICAL FIELD
[0001] The embodiments described herein relate to particular oil
soluble metal additives and use of such metal additives in
lubricating oil formulations to improve antiwear properties of the
formulations.
BACKGROUND
[0002] The next generation of passenger car motor oil and heavy
duty diesel engine oil categories will require equivalent antiwear
properties but with lower levels of phosphorus and sulfur in the
formulations in order to reduce contamination of more stringent
pollution control devices. It is well known that sulfur and
phosphorus containing additives impart antiwear properties to a
finished oil, and also may poison or otherwise reduce the
effectiveness of pollution control devices.
[0003] Zinc dialkyl dithiophosphates ("Zn DDPs") have been used in
lubricating oils for many years. Zn DDPs also have good antiwear
properties and have been used to pass cam wear tests, such as the
Seq IVA and TU3 Wear Test. Many patents address the manufacture and
use of Zn DDPs including U.S. Pat. Nos. 4,904,401; 4,957,649;
6,114,288, all of which are incorporated herein by reference in
their entirety.
[0004] Sulfur-containing antiwear are also well known and include
dihydrocarbyl polysulfides; sulfurized olefins; sulfurized fatty
acid esters of both natural and synthetic origins; trithiones;
sulfurized thienyl derivatives; sulfurized terpenes; sulfurized
polyenes; sulfurized Diels-Alder adducts, etc. Specific examples
include sulfurized isobutylene, sulfurized diisobutylene,
sulfurized triisobutylene, dicyclohexyl polysulfide, diphenyl
polysulfide, dibenzyl polysulfide, dinonyl polysulfide, and
mixtures of di-tert-butyl polysulfides such as mixtures of
di-tert-butyl trisulfide, di-tert-butyl tetrasulfide and
di-tert-butyl pentasulfide, among others. Of the foregoing,
sulfurized olefins are used in many applications. Methods of
preparing sulfurized olefins are described in U.S. Pat. Nos.
2,995,569; 3,673,090; 3,703,504; 3,703,505; 3,796,661; and
3,873,454. Also useful are the sulfurized olefin derivatives
described in U.S. Pat. No. 4,654,156. Other sulfur-containing
antiwear agents are described in U.S. Pat. Nos. 4,857,214,
5,242,613, and 6,096,691.
[0005] A need exists for a lubricating additive that provides
excellent antiwear properties and is more compatible with pollution
control devices used for automotive and diesel engines.
SUMMARY OF THE EMBODIMENTS
[0006] In one embodiment herein is presented a lubricated surface
exhibiting reduce wear. The lubricated surface includes an antiwear
coating of a lubricant composition containing a base oil of
lubricating viscosity and an amount of a hydrocarbon soluble
titanium compound effective to provide a reduction in surface wear
greater than a surface wear of a lubricant composition devoid of
the hydrocarbon soluble titanium compound.
[0007] In another embodiment, there is provided a vehicle having
moving parts and containing a lubricant for lubricating the moving
parts. The lubricant includes an oil of lubricating viscosity and
an amount of antiwear agent providing from about 50 to about 500
parts per million titanium in the form of a hydrocarbon soluble
titanium compound.
[0008] In yet another embodiment there is provided a fully
formulated lubricant composition. The lubricant composition
includes a base oil component of lubricating viscosity, an amount
of hydrocarbon soluble titanium-containing agent providing from
about 50 to about 500 parts per million of a titanium metal which
is sufficient to reduce an amount of phosphorus or sulfur antiwear
agent in the lubricant composition for substantially equivalent
wear performance in the absence of the titanium-containing
agent.
[0009] A further embodiment of the disclosure provides a method of
lubricating moving parts with a lubricating oil exhibiting
increased antiwear properties. The method includes using as the
lubricating oil for one or more moving parts a lubricant
composition containing a base oil and an antiwear additive. The
antiwear additive contains a hydrocarbyl fluid and an amount of
hydrocarbon soluble titanium compound providing from about 50 to
about 500 parts per million titanium in the lubricating oil.
[0010] As set forth briefly above, embodiments of the disclosure
provide an antiwear additive including a hydrocarbon soluble
titanium compound that may significantly improve the antiwear
performance of a lubricant composition thereby enabling a decrease
in the amount of phosphorus and sulfur antiwear additives required
for equivalent antiwear performance. The additive may be mixed with
an oleaginous fluid that is applied to a surface to reduce surface
wear. In other applications, the additive may be provided in a
fully formulated lubricant composition. The additive is
particularly directed to meeting the currently proposed GF-4
standards for passenger car motor oils and PC-10 standards for
heavy duty diesel engine oil.
[0011] The compositions and methods described herein are
particularly suitable for reducing contamination of pollution
control devices on motor vehicles or, in the alternative, the
compositions are suitable for improving the performance of antiwear
agents in lubricant formulations. Other features and advantages of
the compositions and methods described herein may be evident by
reference to the following detailed description which is intended
to exemplify aspects of the preferred embodiments without intending
to limit the embodiments described herein.
[0012] It is to be understood that both the foregoing general
description and the following detailed description are exemplary
and explanatory only and are intended to provide further
explanation of the embodiments disclosed and claimed.
DETAILED DESCRIPTION OF EMBODIMENTS
[0013] In one embodiment is presented a novel composition useful as
a component in lubricating oil compositions. The composition
comprises a hydrocarbon soluble titanium compound that may be used
in addition to or as a partial replacement for conventional
antiwear additives containing phosphorus and sulfur.
[0014] The primary component of the additives and concentrates
provided for lubricant compositions is a hydrocarbon soluble
titanium compound. The term "hydrocarbon soluble" means that the
compound is substantially suspended or dissolved in a hydrocarbon
material, as by reaction or complexation of a reactive titanium
compound with a hydrocarbon material. As used herein, "hydrocarbon"
means any of a vast number of compounds containing carbon,
hydrogen, and/or oxygen in various combinations.
[0015] Examples of suitable titanium compounds for use according to
the disclosure, include, but are not limited to, titanium compounds
derived from acids, alcohols, and glycols, such as titanium
carboxylates, titanium phenates, titanium alkoxides, titanium
sulfonates, and the like. Such compounds may contain from about 5
to about 200 or more carbon atoms in a hydrocarbyl component of the
compound.
[0016] The term "hydrocarbyl" refers to a group having a carbon
atom directly attached to the remainder of the molecule and having
predominantly hydrocarbon character. Examples of hydrocarbyl groups
include: [0017] (1) hydrocarbon substituents, that is, aliphatic
(e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl,
cycloalkenyl) substituents, and aromatic-, aliphatic-, and
alicyclic-substituted aromatic substituents, as well as cyclic
substituents wherein the ring is completed through another portion
of the molecule (e.g., two substituents together form an alicyclic
radical); [0018] (2) substituted hydrocarbon substituents, that is,
substituents containing non-hydrocarbon groups which, in the
context of the description herein, do not alter the predominantly
hydrocarbon substituent (e.g., halo (especially chloro and fluoro),
hydroxy, alkoxy, mercapto, alkylmercapto, nitro, nitroso, and
sulfoxy); [0019] (3) hetero-substituents, that is, substituents
which, while having a predominantly hydrocarbon character, in the
context of this description, contain other than carbon in a ring or
chain otherwise composed of carbon atoms. Hetero-atoms include
sulfur, oxygen, nitrogen, and encompass substituents such as
pyridyl, furyl, thienyl and imidazolyl. In general, no more than
two, preferably no more than one, non-hydrocarbon substituent will
be present for every ten carbon atoms in the hydrocarbyl group;
typically, there will be no non-hydrocarbon substituents in the
hydrocarbyl group.
[0020] Examples of useful titanium alkoxides include, but are not
limited to, C.sub.1-C.sub.20 alkyl titanates, such as octylene
glycol titanate, butyl titanate, polybutyl titanate,
tetra-isopropyl titanate, tetranonyl titanate, and tetra iso-octyl
titanate. Aryl and aralkyl esters of titanium may also be used such
as tetraphenyl titanates, tetrabenzyl titanates, dietheyl diphenyl
titanates, and the like. Examples of suitable titanates may be
found in U.S. Pat. Nos. 2,160,273; 2,960,469; and 6,074,444.
[0021] Titanium salts of carboxylic acids may be made by reacting
the alkali metal salt aqueous solution of an organic acid, the
amine salt aqueous solution of the organic acid, and/or the
ammonium salt aqueous solution of the organic acid with the aqueous
solution of titanium tetrachloride and subsequently oxidizing the
reaction product. Examples of titanium salts of carboxylic acids
include, but are not limited to, titanium salts of formic, acetic,
proprionic, buyric, valeric, caproic, caprylic, lauric, myristic,
palmitic, stearic, oleic, linoleic, linolenic,
cyclohexanecarboxylic, phenylacetic, benzoic, neodecanoic acids,
and the like.
[0022] Other titanium organic compounds that may be used include,
but are not limited to titanium phenates, titanium salicylates,
titanium phosphates, and sulphurized titanium phenates, wherein
each aromatic group has one or more aliphatic groups to impart
hydrocarbon solubility; the basic salts of any of the foregoing
phenols or sulphurized phenols (often referred to as "overbased"
phenates or "overbased sulphurized phenates"); and titanium
sulfonates wherein each sulphonic acid moiety is attached to an
aromatic nucleus which in turn usually contains one or more
aliphatic substituents to impart hydrocarbon solubility; the highly
basic salts of any of the foregoing sulfonates (often referred to
as "overbased sulfonates". The sulfonates, salicylates, phosphates,
and phenates described above may include sodium, potassium,
calcium, and/or magnesium sulfonates and phenates in combination
with the titanium sulfonates, salicylates, phosphates, and
phenates.
[0023] The hydrocarbon soluble titanium compounds of the
embodiments described herein are advantageously incorporated into
lubricating compositions. The titanium compounds may be added
directly to the lubricating oil composition. In one embodiment,
however, they are diluted with a substantially inert, normally
liquid organic diluent such as mineral oil, synthetic oil (e.g.,
ester of dicarboxylic acid), naptha, alkylated (e.g., C10-C13
alkyl) benzene, toluene or xylene to form an additive concentrate.
The titanium additive concentrates usually contain from about 0% to
about 99% by weight diluent oil.
[0024] In the preparation of lubricating oil formulations it is
common practice to introduce the additives in the form of 1 to 99
wt. % active ingredient concentrates in hydrocarbon oil, e.g.
mineral lubricating oil, or other suitable solvent. Usually these
concentrates may be added with 0.05 to 10 parts by weight of
lubricating oil per part by weight of the additive package in
forming finished lubricants, e.g. crankcase motor oils. The purpose
of concentrates, of course, is to make the handling of the various
materials less difficult and awkward as well as to facilitate
solution or dispersion in the final blend.
[0025] Lubricant compositions made with the hydrocarbon soluble
titanium additive described above are used in a wide variety of
applications. For compression ignition engines and spark ignition
engines, it is preferred that the lubricant compositions meet or
exceed published GF-4 or API-CI-4 standards. Lubricant compositions
according to the foregoing GF-4 or API-CI-4 standards include a
base oil and an oil additive package to provide a fully formulated
lubricant. The base oil for lubricants according to the disclosure
is an oil of lubricating viscosity selected from natural
lubricating oils, synthetic lubricating oils and mixtures thereof.
Such base oils include those conventionally employed as crankcase
lubricating oils for spark-ignited and compression-ignited internal
combustion engines, such as automobile and truck engines, marine
and railroad diesel engines, and the like.
[0026] Natural oils include animal oils and vegetable oils (e.g.,
castor oil, lard oil), liquid petroleum oils and hydrorefined,
solvent-treated or acid-treated mineral lubricating oils of the
paraffinic, naphthenic and mixed paraffinic-naphthenic types. Oils
of lubricating viscosity derived from coal or shale are also useful
base oils. The synthetic lubricating oils used in this invention
include one of any number of commonly used synthetic hydrocarbon
oils, which include, but are not limited to, poly-alpha-olefins,
alkylated aromatics, alkylene oxide polymers, interpolymers,
copolymers and derivatives thereof here the terminal hydroxyl
groups have been modified by esterification, etherification etc,
esters of dicarboxylic acids and silicon-based oils.
[0027] Fully formulated lubricants conventionally contain an
additive package, referred to herein as a dispersant/inhibitor
package or DI package, that will supply the characteristics that
are required in the formulations. Suitable DI packages are
described for example in U.S. Pat. Nos. 5,204,012 and 6,034,040 for
example. Among the types of additives included in the additive
package are detergents, dispersants, friction modifiers, seal swell
agents, antioxidants, foam inhibitors, lubricity agents, rust
inhibitors, corrosion inhibitors, demulsifiers, viscosity index
improvers, and the like. Several of these components are well known
to those skilled in the art and are preferably used in conventional
amounts with the additives and compositions described herein.
[0028] For example, ashless dispersants include an oil soluble
polymeric hydrocarbon backbone having functional groups that are
capable of associating with particles to be dispersed. Typically,
the dispersants comprise amine, alcohol, amide, or ester polar
moieties attached to the polymer backbone often via a bridging
group. The ashless dispersants may be, for example, selected from
oil soluble salts, esters, amino-esters, amides, imides, and
oxazolines of long chain hydrocarbon substituted mono and
dicarboxylic acids or their anhydrides; thiocarboxylate derivatives
of long chain hydrocarbons; long chain aliphatic hydrocarbons
having a polyamine attached directly thereto; and Mannich
condensation products formed by condensing a long chain substituted
phenol with formaldehyde and a polyalkylene polyamine.
[0029] Viscosity modifiers (VM) function to impart high and low
temperature operability to a lubricating oil. The VM used may have
that sole function, or may be multifunctional.
[0030] Multifunctional viscosity modifiers that also function as
dispersants are also known. Suitable viscosity modifiers are
polyisobutylene, copolymers of ethylene and propylene and higher
alpha-olefins, polymethacrylates, polyalkylmethacrylates,
methacrylate copolymers, copolymers of an unsaturated dicarboxylic
acid and a vinyl compound, inter polymers of styrene and acrylic
esters, and partially hydrogenated copolymers of styrene/isoprene,
styrene/butadiene, and isoprene/butadiene, as well as the partially
hydrogenated homopolymers of butadiene and isoprene and
isoprene/divinylbenzene.
[0031] Oxidation inhibitors or antioxidants reduce the tendency of
base stocks to deteriorate in service which deterioration can be
evidenced by the products of oxidation such as sludge and
varnish-like deposits on the metal surfaces and by viscosity
growth. Such oxidation inhibitors include hindered phenols,
alkaline earth metal salts of alkylphenolthioesters having
preferably C.sub.5 to C.sub.12 alkyl side chains, calcium
nonylphenol sulfide, ashless oil soluble phenates and sulfurized
phenates, phosphosulfurized or sulfurized hydrocarbons, phosphorus
esters, metal thiocarbamates and oil soluble copper compounds as
described in U.S. Pat. No. 4,867,890.
[0032] Rust inhibitors selected from the group consisting of
nonionic polyoxyalkylene polyols and esters thereof,
polyoxyalkylene phenols, and anionic alkyl sulfonic acids may be
used.
[0033] A small amount of a demulsifying component may be used. A
preferred demulsifying component is described in EP 330,522. It is
obtained by reacting an alkylene oxide with an adduct obtained by
reacting a bis-epoxide with a polyhydric alcohol. The demulsifier
should be used at a level not exceeding 0.1 mass % active
ingredient. A treat rate of 0.001 to 0.05 mass % active ingredient
is convenient.
[0034] Pour point depressants, otherwise known as lube oil flow
improvers, lower the minimum temperature at which the fluid will
flow or can be poured. Such additives are well known. Typical of
those additives which improve the low temperature fluidity of the
fluid are C.sub.8 to C.sub.18 dialkyl fumarate/vinyl acetate
copolymers, polyalkylmethacrylates and the like.
[0035] Foam control can be provided by many compounds including an
antifoamant of the polysiloxane type, for example, silicone oil or
polydimethyl siloxane.
[0036] Seal swell agents, as described, for example, in U.S. Pat.
Nos. 3,794,081 and 4,029,587, may also be used.
[0037] Each of the foregoing additives, when used, is used at a
functionally effective amount to impart the desired properties to
the lubricant. Thus, for example, if an additive is a corrosion
inhibitor, a functionally effective amount of this corrosion
inhibitor would be an amount sufficient to impart the desired
corrosion inhibition characteristics to the lubricant. Generally,
the concentration of each of these additives, when used, ranges up
to about 20% by weight based on the weight of the lubricating oil
composition, and in one embodiment from about 0.001% to about 20%
by weight, and in one embodiment about 0.01% to about 10% by weight
based on the weight of the lubricating oil composition.
[0038] The titanium compound additives may be added directly to the
lubricating oil composition. In one embodiment, however, they are
diluted with a substantially inert, normally liquid organic diluent
such as mineral oil, synthetic oil, naphtha, alkylated (e.g.
C10-C13 alkyl) benzene, toluene or xylene to form an additive
concentrate. These concentrates usually contain from about 1% to
about 100% by weight and in one embodiment about 10% to about 90%
by weight of the titanium compound.
[0039] Base oils suitable for use in formulating the compositions,
additives and concentrates described herein may be selected from
any of the synthetic or natural oils or mixtures thereof. The
synthetic base oils include alkyl esters of dicarboxylic acids,
polyglycols and alcohols, poly-alpha-olefins, including
polybutenes, alkyl benzenes, organic esters of phosphoric acids,
and polysilicone oils. Natural base oils include mineral
lubrication oils which may vary widely as to their crude source,
e.g., as to whether they are paraffinic, naphthenic, or mixed
paraffinic-naphthenic. The base oil typically has a viscosity of
about 2.5 to about 15 cSt and preferably about 2.5 to about 11 cSt
at 110.degree. C.
[0040] Accordingly, the base oil used which may be used may be
selected from any of the base oils in Groups I-V as specified in
the American Petroleum Institute (API) Base Oil Interchangeability
Guidelines. Such base oil groups are as follows: TABLE-US-00001
Saturates Viscosity Base Oil Group.sup.1 Sulfur (wt. %) (wt. %)
Index Group I >0.03 and/or <90 80 to 120 Group II <0.03
And >90 80 to 120 Group III <0.03 And >90 >120 Group IV
all polyalphaolefins (PAOs) Group V all others not included in
Groups I-IV .sup.1Groups I-III are mineral oil base stocks.
[0041] The additives used in formulating the compositions described
herein can be blended into the base oil individually or in various
sub-combinations. However, it is preferable to blend all of the
components concurrently using an additive concentrate (i.e.,
additives plus a diluent, such as a hydrocarbon solvent). The use
of an additive concentrate takes advantage of the mutual
compatibility afforded by the combination of ingredients when in
the form of an additive concentrate. Also, the use of a concentrate
reduces blending time and lessens the possibility of blending
errors.
[0042] The embodiments provide a lubricating oil for internal
combustion engines in which the concentration of the added
hydrocarbon soluble titanium compound is relatively low, providing
from about 50 to about 500 parts per million (ppm) titanium in
terms of elemental titanium in the oil. In one embodiment, the
titanium compound is present in the lubricating oil compositions in
an amount sufficient to provide from about 100 to about 200 ppm
titanium metal, and in a further embodiment from about 120 to about
180 ppm titanium metal.
[0043] The following example is given for the purpose of
exemplifying aspects of the embodiments and is not intended to
limit the embodiments in any way.
EXAMPLE
[0044] Thirteen fully formulated lubricant compositions were made
and the wear properties of the compositions were compared using a
four ball wear test according to European test code IP-239. Each of
the lubricant compositions contained a conventional DI package
providing 11 percent by weight of the lubricant composition. The DI
package contained conventional amounts of detergents, dispersants,
antiwear additives, friction modifiers, antifoam agents, and
antioxidants. The formulations also contained about 0.1 percent by
weight pour point depressant, about 11.5 percent by weight olefin
copolymer viscosity index improver, about 62 to 63 percent by
weight 150 solvent neutral oil, about 14.5 percent by weight 600
solvent neutral oil. Sample 1 contained no titanium compound.
Samples 2-13 contained titanium compounds in amounts sufficient to
provide about 80 to about 200 ppm titanium metal. The samples was
tested in the lubricant formulation using a four ball wear test at
room temperature, for 60 minutes at an rpm of 1475 using a 40
kilogram weight. The formulations and results are given in the
following table. TABLE-US-00002 Sample Sample Sample Sample Sample
Sample Sample Sample Sample Sample Sample Sample Sample Component 1
2 3 4 5 6 7 8 9 10 11 12 13 DI Package 11.0 11.0 11.0 11.0 11.0
11.0 11.0 11.0 11.0 11.0 11.0 11.0 11.0 Ti-TEN CEN -- 0.170 0.340
-- -- -- -- -- -- -- -- -- -- Ti-2-EHO -- -- -- 0.115 0.230 -- --
-- -- -- -- -- -- KR-TTS -- -- -- -- -- 0.183 0.336 -- -- -- -- --
-- LICA-01 -- -- -- -- -- -- -- 0.173 0.346 -- -- -- -- KR-12 -- --
-- -- -- -- -- -- -- 0.327 0.654 -- -- KR-9S -- -- -- -- -- -- --
-- -- -- -- 0.287 0.575 PPD 0.100 0.100 0.100 0.100 0.100 0.100
0.100 0.100 0.100 0.100 0.100 0.100 0.100 Viscosity index 11.5 11.5
11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 11.5 improver
ESSO 150 solvent 62.90 62.73 62.56 62.78 62.67 62.72 62.53 62.73
62.55 62.57 62.25 62.61 62.32 neutral oil ESSO 600 solvent 14.50
14.50 14.50 14.50 14.50 14.50 14.50 14.50 14.50 14.50 14.50 14.50
14.50 neutral oil Total 100 100 100 100 100 100 100 100 100 100 100
100 100 Ti (ppm) 0 87 167 100 196 91 176 105 205 101 198 102 202 4
ball wear test 0.65 0.42 0.46 0.47 0.46 0.37 0.44 0.34 0.40 0.44
0.42 0.48 0.37
[0045] In the above table, the following legend is used:
[0046] Ti-TEN CEN is a titanium neodecanoate from OM Group, Inc. of
Newark, N.J. and contains about 6.7% by weight titanium metal.
[0047] Ti-2-EHO is titanium 2-ethylhexoxide containing about 8.7%
by weight titanium metal.
[0048] KR-TTS is titanium IV 2-propanolato, tris isooctadecanoato-O
from Kenrich Petrochemicals, Inc. of Bayonne, N.J. and contains
about 5.5% titanium metal.
[0049] LICA-01 is titanium IV 2,2(bis
2-propenolatomethyl)butanolato, tris neodecanoato-O from Kenrich
Petrochemicals, Inc. and contains about 5.8% titanium metal.
[0050] KR-12 is titanium IV 2-propanolato,
tris(dioctyl)phosphato-O, from Kenrich Petrochemicals, Inc. and
contains about 3.1% titanium metal.
[0051] KR-9S is titanium IV 2-propanolato,
tris(dodecyl)benzenesulfanato-O, from Kenrich Petrochemicals, Inc.
and contains about 3.5% titanium metal.
[0052] PPD is a pour point depressant from Afton Chemical
Corporation of Richmond Va., under the trade name HiTEC.RTM.
672.
[0053] As illustrated by the foregoing results, samples 2-13
containing from about 80 to about 200 ppm titanium metal in the
form of a hydrocarbon soluble titanium compound significantly
outperformed a conventional lubricant composition containing no
titanium metal. Sample 1 containing no titanium metal had a wear
scar diameter of about 0.65 millimeters whereas the other samples
containing titanium had wear scar diameters ranging from about 0.35
to about 0.47 millimeters. It is expected that formulations
containing from about 50 to about 500 ppm titanium metal in the
form of a hydrocarbon soluble titanium compound will enable a
reduction in conventional phosphorus and sulfur antiwear agents
thereby improving the performance of pollution control equipment on
vehicles while achieving a similar antiwear performance or
benefit.
[0054] At numerous places throughout this specification, reference
has been made to a number of U.S. patents. All such cited documents
are expressly incorporated in full into this disclosure as if fully
set forth herein.
[0055] The foregoing embodiments are susceptible to considerable
variation in its practice. Accordingly, the embodiments are not
intended to be limited to the specific exemplifications set forth
hereinabove. Rather, the foregoing embodiments are within the
spirit and scope of the appended claims, including the equivalents
thereof available as a matter of law.
[0056] The patentees do not intend to dedicate any disclosed
embodiments to the public, and to the extent any disclosed
modifications or alterations may not literally fall within the
scope of the claims, they are considered to be part hereof under
the doctrine of equivalents.
* * * * *